J Polym Res (2010) 17:347353

DOI 10.1007/s10965-009-9321-8

ORIGINAL PAPER

Defect-free Poly(9,9-bis(2-ethylhexyl)fluorene-2,7-vinylene)
for Polymer Light-Emitting Diode (PLED) Devices
Piched Auragudom & Andrew A. Tangonan & Manoj A. G. Namboothiry &
David L. Carroll & Rigoberto C. Advincula & Sukon Phanichphant & T. Randall Lee

Received: 12 June 2009 / Accepted: 29 June 2009 / Published online: 13 August 2009
# Springer Science + Business Media B.V. 2009

Abstract The -conjugated light-emitting polymer poly

(9,9-bis(2-ethylhexyl)fluorene-2,7-vinylene) (PEHFV),
was synthesized in defect-free form via Horner-Emmons
coupling. The structure and properties of the polymer were
characterized by 1H NMR, 13C NMR, UV-vis, photoluminescence (PL), and electroluminescence (EL) spectroscopies as well as gel permeation chromatography (GPC)
and thermogravimetric analysis (TGA). The weight-average
molecular weight (Mw) and polydispersity of the PEHFV
were 34,000 g/mol and 2.3, respectively. The UV-vis
spectra showed absorption maxima at 425 and 452 nm,
and the PL emission spectra showed a maximum at 505 nm
with a shoulder at 541 nm. The polymer was soluble in
common organic solvents and easily spin-coated on
indium-tin oxide (ITO)-coated glass substrates. A doublelayer light-emitting device with an ITO/PEDOT:PSS/PFV/
Al configuration was fabricated. The turn-on voltage for the
PEHFV device was observed at 3.0 V.

P. Auragudom (*) : S. Phanichphant

Department of Chemistry and The Center for Innovation
in Chemistry (PERCH-CIC), Faculty of Science,
Chiang Mai University,
Chiang Mai 50200, Thailand
e-mail: piched@chiangmai.ac.th
A. A. Tangonan : R. C. Advincula : T. R. Lee (*)
Department of Chemistry,
University of Houston,
4800 Calhoun Road,
Houston, TX 77204-5003, USA
e-mail: trlee@uh.edu
M. A. G. Namboothiry : D. L. Carroll
The Center for Nanotechnology and Molecular Materials,
Department of Physics, Wake Forest University,
Winston-Salem, NC 27109, USA

Keywords Polymer light-emitting diode (PLED) .

Poly(fluorene vinylene)(PFV) . Defect-free .
Electroluminescence

Introduction
Polymer light-emitting diodes (PLEDs) are promising
devices, especially for next generation active matrix displays. Solution deposition techniques, homogeneous large
area thin films, reduced manufacturing process complexity,
low-cost, high luminescence efficiency, large spectral
range, and relatively simple device structures are some of
the main reasons for an increased interest in polymer
materials for LEDs [1]. Among the -conjugated polymers, poly(p-phenylene vinylene) (PPV) [2] and poly(9,9dialkylfluorene) (PF) [3] and their derivatives have been
widely used for polymer LEDs. For PFs, few systematic
studies have explored side-branching effects, [4] including
possible effects of side-branching with respect to synthesis,
MW and polydispersity, solubility, rheological properties,
and end capping. This fact is surprising given that poly(2,7fluorene)s with alkyl substituents attached to the C-9
position have been widely reported since 1989 [57]. In
the case of PPV, different side-chain combinations of
dialkoxy PPV derivatives showed an increase in EL
efficiency with the length of the longest side chain [8].
The increase in efficiencies may be related to an increased
chain-to-chain separation.
The goal of combining the attractive properties PF and
PPV can be manifested in the study of polyfluorene
vinylenes (PFVs). For both PPV and PFV, it is well known
that the Gilch polymerization route has several advantages,
including high yield, high molecular weight, low polydispersity, and facile design and availability of the monomers.

348

The Gilch route, however, suffers from the problem of

having saturated defects along the chain backbone (predominantly tolane-bisbenzyl-type moieties analogous to
those commonly found in samples of PPV) [9, 11]. Other
published routes to PFVs are surprisingly few, although
Heck coupling [10, 12, 14]. and acyclic diene metathesis
(ADMET) polymerizations have been reported [15]. Both
of these methods, however, require air-free conditions and
the use of costly transition metal catalysts.
In the present study, we report the use of a simple
Horner-Emmons reaction utilizing aromatic dialdehydes
and diphosphonates to generate defect-free poly(9,9- bis
(2-ethylhexyl) fluorene-2,7-vinylene) (PEHFV). The synthetic route [16, 17] and polymer structures are shown in
Scheme 1 [18]. The samples obtained were of high
molecular weight with no detectable saturated defects along
the conjugated backbone [9, 11, 16, 17]. PLED devices
with the defect-free PEHFV as the light-emitting layer were
prepared and their electro-optical properties were characterized.

Experimental
Materials Fluorene, n-butyllithium (2.5 M in hexane),
1-bromooctane, potassium tert-butoxide (1 M solution in
THF), bromine, copper cyanide, diisobutylaluminum hydride (DIBAL-H) in toluene, sodium borohydride, thionyl
chloride, and triethyl phosphite were purchased from
Aldrich Chemical Co. and used without further purification
unless otherwise noted. THF was dried and purified by
fractional distillation over sodium/benzophenone and handled in a moisture-free atmosphere. Dichloromethane and
DMF were distilled over CaH2, and column chromatography was performed using silica gel (Merck, 250430
mesh).
Syntheses of monomers and polymers The strategy used to
synthesize and polymerize the custom-designed monomers is illustrated graphically in Scheme 1. Details of
analogous synthetic procedures can be found in a previous
report [16].
9,9-Bis(2-ethylhexyl)fluorene (1). Compound 1 was
obtained as a pale brown oil (99%). 1H NMR (300 MHz,
CDCl3): 7.72 (d, J=7.3 Hz, 2H, aromatic), 7.41 (d, 2H,
J=7.3 Hz, 2H, aromatic), 7.237.37 (m, 4H, aromatic),
2.03 (m, 4H, -CH2), 1.28 (m, 2H, -CH), 0.600.97
(m, 16H, alkyl), 0.54 (t, J=7.4 Hz, 12H). 13C NMR
(75 MHz, CDCl3): 151.1, 141.9, 127.2, 126.9, 124.6,
120.1, 55.4, 45.1, 34.2, 28.7, 27.4, 23.2, 14.5, 10.8.
2,7-Dibromo-9,9-bis(2-ethylhexyl)fluorene (2). Under argon, 39 g (0.10 mol) of 9,9-bis(2-ethylhexyl)fluorene was

P. Auragudom et al.

placed in a 500 mL round-bottomed flask. After the

addition of 300 mL of dry DMF, 15 mL (0.30 mol) of
bromine was added slowly. The mixture was allowed to
react for 20 h at rt, and then saturated NaHSO3 was added
until the red color disappeared. The mixture was extracted
three times with 200 mL of diethyl ether. The organic
extracts were combined, washed with brine, and dried with
magnesium sulfate. Upon filtering the solution and evaporating the solvent, a viscous yellow oil was obtained and
used without further purification or analysis.
2,7-Dicyano-9,9-bis(2-ethylhexyl)fluorene (3). Pale yellow crystalline 3 (0.43 g, 54%) was obtained upon removal
of the solvent under vacuum. 1H NMR (300 MHz, CDCl3):
7.85 (d, J=8.2 Hz, 2H, aromatic), 7.677.73 (m, 4H,
aromatic), 2.03 (m, 4H, -CH2), 0.581.00 (m, 22H, alkyl),
0.260.56 (m, 8H). 13C NMR (75 MHz, CDCl3): 152.5,
144.1, 132.1, 128.4, 121.9, 119.6, 111.9, 56.3, 44.8, 35.3,
34.1, 28.5, 27.4, 23.1, 14.4, 10.7.
9,9-Bis(2-ethylhexyl)fluorene-2,7-dicarboxaldehyde (4).
Compound 4 was obtained as a yellow oil (0.76 g, 85%).
1
H NMR (300 MHz, CDCl3): 10.09 (s, 2H, CHO), 7.89
8.00 (m, 6H, aromatic), 2.10 (m, 4H, -CH2), 0.570.94
(m, 22H, alkyl), 0.360.52 (m, 8H). 13C NMR (75 MHz,
CDCl3): 192.5, 153.3, 146.2, 136.4, 130.5, 125.3, 121.8,
55.9, 44.8, 35.3, 34.1, 28.5, 27.5, 23.1, 14.4, 10.7.
2,7-Bis(hydroxymethyl)-9,9-bis(2-ethylhexyl)fluorene
(5). Compound 5 was obtained as colorless crystals (0.78 g,
87%). 1H NMR (300 MHz, CDCl3): 7.65 (d, J=7.7 Hz,
2H), 7.38 (s, 2H), 7.30 (d, J=7.7 Hz, 2H), 4.74 (s, 4H,
CH2OH), 1.97 (m, 4H), 1.59 (s, 2H, CH2OH), 0.590.98
(m, 22H, alkyl), 0.420.56 (m, 8H). 13C NMR (75 MHz,
CDCl3): 151.9, 141.4, 136.3, 128.3, 125.1, 120.2, 55.5,
47.5, 44.8, 35.2, 34.5, 28.7, 27.5, 23.1, 14.5, 10.7.
2,7-Bis(chloromethyl)-9,9-bis(2-ethylhexyl)fluorene (6).
Compound 6 was obtained as a white crystalline solid
(31.5 g, 93%). 1H NMR (300 MHz, CDCl3): 7.65 (d, J=
7.7 Hz, 2H), 7.41 (s, 2H), 7.32 (d, J=7.7 Hz, 2H), 4.66
(s, 4H, CH2Cl), 1.99 (m, 4H), 0.620.99 (m, 22H, alkyl),
0.370.56 (m, 8H). 13C NMR (75 MHz, CDCl3): 151.9,
141.4, 136.5, 128.0, 125.1, 120.4, 55.5, 47.4, 44.8, 35.2,
34.5, 28.7, 27.5, 23.2, 14.5, 10.8.
2,7-Bis(methylenediethylphosphate)-9,9-bis(2-ethylhexyl)fluorene (7). Compound 7 was obtained in crude form
(2.2 g, 97%). 1H NMR (300 MHz, CDCl3): 7.58 (d, J=
7.7 Hz, 2H), 9.29 (s, 2H), 7.23 (d, J=7.7 Hz, 2H), 3.87
4.19 (m, 8H, OCH2CH3), 3.20 (d, JPH = 21.8 Hz, CH2P),
1.95 (m, 4H), 1.25 (m, 12H, OCH2CH3), 0.590.98 (m,
22H, alkyl), 0.400.58 (m, 8H) 13C NMR (75 MHz,
CDCl3): 151.6, 140.3, 130.2, 128.9, 126.0, 120.0, 62.5,
55.3, 45.5, 35.5, 35.1, 33.8, 28.6, 27.2, 23.2, 16.9, 14.5,
10.6.
Poly(9,9-bis(2-ethylhexyl)fluorene-2,7-vinylene) via
Horner-Emmons Coupling. As shown in Scheme 1, the

Defect-free poly(9,9-bis(2-ethylhexyl)fluorene-2,7-vinylene)

349

Scheme 1 Strategy for synthesizing monomers and polymers

dicarboxyaldehyde (0.99 g, 1.4 mmol) and crude 7 were

dissolved in 50 mL of anhydrous DMF under nitrogen. To
this solution, potassium tert-butoxide (10 mL of a 1 M
solution in THF) was added. The reaction was stirred
overnight at rt under nitrogen. The polymer was precipitated into 400 mL of methanol, and the mixture was
centrifuged. The supernatant was decanted, and the poly-

mer residue was re-dissolved in a minimum amount of

THF. The crude polymer was then successively reprecipitated using methanol, isopropyl alcohol, and hexane
to remove small molecule impurities and/or oligomers. The
final product was dried under vacuum overnight to afford
PFV as a bright yellow-green solid (79%). 1H-NMR
(300 MHz, CDCl3): 7.167.83 (m, 8H, aromatic &

350

P. Auragudom et al.

vinylic), 1.942.21 (m, 4H, -CH2), 0.741.13 (m, 18H,

alkyl), 0.620.75 (m, 6H), 0.430.62 (m, 6H).
Measurements 1H and 13C NMR spectra were recorded
using a General Electric QE-300 spectrometer (300 MHz),
and chemical shifts were recorded in ppm. The data were
processed using NUTSNMR Utility Transform Software
(Acron NMR). The UV-vis spectra were recorded on a
Perkin Elmer Lambda 19 UV-VIS-NIR spectrophotometer
with baseline corrections and normalizations carried out
using WinLab software. Photoluminescence spectra were
collected on a USB2000 Miniature Fiber Optic Spectrometer. We used OOIBase32 Spectrometer Operating Software
to collect and display data obtained from the USB2000
instrument.
Molecular weights and polydispersities of the polymers
were determined by gel permeation chromatography (GPC)
relative to calibrated polystyrene standards using a Waters
Styragel HR 5E column (7.8300 mm) and both a Waters
410 Differential Refractometer and a Waters 996 Photodiode Array Detector. Thermogravimetric analysis (TGA)
data were collected using a Perkin-Elmer TGA-7 under
nitrogen, while differential scanning calorimetry (DSC)
data were collected using a Perkin-Elmer DSC-7 under
nitrogen at a heating rate of 10 C/min. Clean ITO was
treated with O2 plasma for 100 to 210 s before use. Films of
PEDOT:PSS (Baytron) were prepared by spin casting a
solution containing 0.5% by weight of the polymer in THF
at a speed of 1,500 rpm for 120 s under ambient conditions.
A film of aluminum was then deposited on top of the
polymer film through a shadow mask by vacuum evaporation at a pressure of less than 4106 Torr. For characterization of the device performance, current-voltage (IV)
curves were measured with a Keithley 236 programmable
source meter.

Fig. 1 1H-NMR spectrum of PEHFV prepared by Horner-Emmons

coupling

gated backbone [16, 17]. The molecular structures of the

monomer and the corresponding polymer were identified
by 1H-NMR spectroscopy. Figure 1 highlights the region
between 0.0 and 3.5 ppm for PEHFV, showing no
detectable resonances near 3.1 ppm that are characteristic
of saturated defects [9, 11, 16]. We thus conclude that our
synthesis strategy gives PEHFV with no detectable
saturated defect along the conjugated backbone. In the case
of Gilch polymerization [16], a small resonance at 3.1 ppm
is typically observed [11, 16]; this resonance has been
assigned to ArCH2CH2Ar defects along the chain
backbone. The PEHFV also showed a monomodal distri-

Results and discussion

Synthesis and characterization of monomers and
polymers Fluorene-based polymers can be easily functionalized with substituents at the C-9 position. The electronic
and optical properties of the conjugated polymer can then
be tuned by modifying the structure of the polymer
backbone, which can shift the energy levels of the HOMO
and LUMO. For poly(9,9-bis(2-ethylhexyl)fluorene- 2,
7-vinylene), we adjusted the energy levels by introducing
a vinylene group via Horner-Emmons coupling of the
aromatic dialdehydes and diphosphonates shown in
Scheme 1. The Horner-Emmons reaction was used because
we wished to generate an alternating fluorene vinylene
homopolymer with no saturated defects along the conju-

Fig. 2 TGA and DSC thermograms of PEHFV prepared by HornerEmmons coupling

Defect-free poly(9,9-bis(2-ethylhexyl)fluorene-2,7-vinylene)

bution with a number-average molecular weight (Mn)

of 34,000 and a weight-average molecular weight (Mw)
of 78,000 to give a PDI=2.3 as determined by GPC with
THF as the eluent.
The thermal behavior of the resulting polymers was
investigated by TGA. Shown in Fig. 2 are the TGA
thermograms of the synthesized polymers obtained under
nitrogen. The PEHFV samples exhibited good thermal
stabilities, losing their weight at less than 3% on heating to
approximately 400 C under nitrogen, but lose about 68%
of their weight at 450480 C. The high thermal stability of
the present polymers should prevent chain deformation and
degradation of the emitting layer by current-induced
heating during the operation of EL devices. On the basis
of these results, it might be expected that the PEHFV
synthesized in the present work, which has a highly rigid
backbone and long flexible alkyl groups on the side chain,
would form liquid crystalline structures. The DSC measurements showed glass transitions at around 170230 C for
this PFV with a branched-chain substituent at the C-9
position. However, we found no evidence of a significant
mesophase or liquid crystalline texture in the analyses by
DSC and polarized microscopy.
Optical and photoluminescence properties The UV-vis
absorption spectra of the PEHFV prepared via HornerEmmons polymerization at a concentration of 4.8105 M
is shown in Fig. 3. The sample of PEHFV exhibits a broad
absorption with three discernable max bands having
increasing intensities at 400 nm, 425 nm, and 452 nm,
respectively. These bands can be attributed to -*
transitions of the conjugated backbone that are vibrationally
split and consistent with extended delocalization between
the fluorene and vinylene units [11, 12, 14, 19].

351

Fig. 4 Photoluminescence of PEHFV in solid form (powder) at room

temperature (excitation at 370 nm)

We note further that the absorption spectrum for the

PEHFV produced here is identical to that reported for other
PFVs prepared via ADMET [15] and Horner-Emmons
coupling [16, 17]. Taken together with the NMR data above,
we conclude that PFVs prepared via Horner-Emmons
coupling and ADMET polymerization afford polymers that
are free of saturated defects along the backbone.
The fluorescence (FL) spectrum is characterized by three
discernable emission bands having decreasing intensities at
453 nm, 483 nm, and 515 nm, respectively; the pattern of
these bands also reflects the influence of vibronic coupling
[12, 14, 19]. The photoluminescence (PL) spectrum
obtained for the sample of PEHFV deposited as a film is
shown in Fig. 4. The major emission bands in the spectrum
appear at 475 nm, 505 nm, 540 nm, and 575 nm. The red
shift of these vibronically coupled maxima relative to those
in solution is consistent with previous studies of PFVs and
related materials [12, 14, 19].
Electroluminescence and current-voltage-luminescence
(I-V-L) characteristics The LED structure consisted of an

Fig. 3 Absorption spectra and fluorescence (1.0106 M, excitation

at 428 nm) in THF at room temperature of PEHFV prepared by
Horner-Emmons coupling

Fig. 5 Current and electroluminescence versus voltage profile of the

ITO/PEDOT:PSS/PEHFV emitting layer/Al device

352

aluminum contact on the surface of the polymer, which was

spun-cast on the ITO surface from a solution of PEHFV in
THF. Aluminum was then deposited on the surface by
vacuum evaporation at pressures of 106 Torr, yielding a
circular active layer with a diameter of 0.075 cm2. Figure 5
show the current-electric field strength (I-V-L) and the
luminescence-electric field strength (L-V-L) characteristics,
respectively, of a single-layer light-emitting diode consisting of ITO/PEDOT:PSS/PFV/Al. The current was observed
to increase with increasing forward bias voltage, which
indicated typical rectifying characteristics. The IV data
consisted of a linear plot, but for the 06 V range only. The
plot in Fig. 5 shows that the device is a typical diode
because the IV curve increases exponentially with voltage.
The turn-on voltage is readily apparent at 3.0 V collected
with a photomultiplier tube (PMT) simultaneously with the
collection of the IV data. The EL was measured for a
PEHFV polymer LED over the full range of voltages,
including the turn-on voltage and the breakdown voltage.
Figure 5 also shows the ELV data, but again for the 06 V
range only. The ELV curve increases exponentially with
voltage and then levels off at higher voltages (and
correspondingly higher current densities), which is consistent with the behavior reported for related OLED devices
[20]. The turn-on voltage is again readily apparent at 3.0 V,
which is relatively low (good), considering that the device
was prepared under ambient conditions. The PEHFV showed
high EL power at low threshold voltage due to the enhanced
p-electron delocalization of the fluorene group. Finally, we
calculated the luminous efficiency to be 6.5 cd/A at an
operating voltage of 4 V. Importantly, the magnitude of the
observed electroluminescence is more than 100 times greater
that found in commercial OLED-based displays [21].
It is known that the contacts between the polymer and
the electrodes strongly influence device efficiency. One
optimization strategy is to modify the ITO surface with a
thin layer of conducting polymer such as polyaniline [22]
or poly(3,4-ethylene dioxythiophene) (PEDOT) [23]. The
presence of a thin PEDOT interlayer can improve the
device efficiency by an order of magnitude or more.
The fluorene and vinylene repeat units influence both the
HOMO and the LUMO energy levels. These energy levels
realize efficient hole and electron injection from both
electrodes [24].

Conclusions
Horner-Emmons coupling proved to be an efficient synthetic route for the preparation of electroluminescent

P. Auragudom et al.

PEHFV. UV-vis absorption spectra in THF of the PEHFV

showed dual absorption maxima at 425 and 452 nm
attributed to -* transitions of the conjugated backbone.
Upon excitation in THF, the polymer exhibited a greenish
fluorescence (max emission = 463 nm with shoulder at
496 nm). Similarly, photoluminescence spectra of powder
samples showed max emission = 505 nm with a shoulder at
540 nm. The PEHFV samples showed high thermal
stability up to 400 C and exhibited a high glass transition
temperature, which might be key in preventing deformation
and degradation of the emitting layer by current-induced
joule heating during the operation of PEHFV-based
electroluminescence devices.
Acknowledgments This research was supported by Chiang Mai
University, the Reverse Brain Drain Project (RBD), The National
Science and Technology Development Agency, Ministry of Science
and Technology, Thailand, and the Center for Innovation in Chemistry
(PERCH-CIC). Additional support for work performed at the
University of Houston was provided by the Texas Center for
Superconductivity and the Robert A. Welch Foundation (Grant E1320). David L Carroll acknowledges funding from AFOSR grant
number FA9550-04-1-0161.

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